1242029 九、發明說明： 本發明關於一種耳产人从^ ‘ ^ ^ ^ ^ 種XK合物組合物，其包含聚合物基質和含 夕氧烷添加劑，該組合物可形成已熟化的矽酮彈性體可黏 於其上之塑膠物。从 ^ σσ /物叩，特別是藉氫矽烷基化反應所熟化的矽 阳彈性體，關於一種從該聚合物組合物製備塑膠物品的方 、及關於3石夕氧燒添加劑在該聚合物組合物的 用途。 …用上理想地將石夕酮彈性體塗覆在塑膠基質 上例如，在密封和襯墊領域上，可在塑膠物質上形成一 由夕_彈n體所製成的塾圈。但是’石夕_彈性體對塑膠 基貝的黏著力不好，為了石夕_彈性體對塑膠基質的黏著力 經常需要改良相彈性體和/或塑膠基質表面。石夕酮彈性體 和/或塑膠基質表面的改良通常可藉助黏劑的使用而達 到，冒使用石夕院達到此目的。塑膠基質表面的改良，例如 可藉將助黏劑塗覆在表面，或者更普遍地在聚合物溶化物 形成塑膠基質之前將助黏劑加入其中而達到。若將助黏劑 力入承&物熔化物^，若欲促進其與經塗覆之石夕綱彈性體 的黏著力，助黏劑必須潛移至聚合物基質表面上。我們已 發現當使用矽烷助黏劑時，此潛移並非一直發生令人滿意 的程度，造成經塗覆之矽酮彈性體的黏度不佳。 美國專利第4,814,231號和第4,686，124號揭示熱塑性樹脂 -矽酮複合物’其中該樹脂包含一種有機氫聚矽氧烷如末端 為乙烯基之有機氫聚矽氧烷以幫助該樹脂對另化熟化之矽 酮組合物的黏著力。 59243-930714.doc 1242029 第一方面，根據本發明，係提供一種聚合物組合物，其 包含聚合物基質和實質上不與聚合物基質相容的矽氧烷添 加劑，其中該添加劑的矽氧烷具有羥基、烷氧基或環氧基 官能基和一個可與^夕酮彈性體形成組合物鍵結的官能基， 其中矽酮彈性體形成組合物可藉氫矽烷基化反應熟化。 因此，本發明提供一種可形成塑膠物品的聚合物組合 物，該組合物可藉簡單地混合添加劑與聚合物基質熔化 物，接著使聚合物組合物成形以形成矽酮彈性體可黏於其 上的塑膠基質而製得。與由不含用於本發明之含矽氧烷添 加劑之聚合物熔化物所製成的塑膠基質相比，根據本發明 聚合物組合物另外具有由其所製成的塑膠基質容易脫模的 優點。 用於本發明之含矽氧烷添加劑實質上與聚合物基質不相 容。在此’’實質上不相容π指添加劑會潛移至聚合物組合物 的表面使該添加劑與可藉氫矽烷基化反應熟之矽酮彈性體 形成組合物結合，但是添加劑與聚合物基質間需要一些相 容性使其不會發生添加劑與聚合物基質完全分離，當添加 劑潛移然後只與矽酮彈性體而不會與塑膠基質鍵結，所以 造成黏著力差。添加劑應作為塑膠基質和矽酮彈性體分子 間的連接物。 適合用於根據本發明聚合物組合物之聚合物基質在技術 上是為人所熟知的，其包括聚砜、聚苯、聚醚酮、聚亞胺、 聚酯、聚乙烯、聚丙烯及酚和環氧基的樹脂類，以聚伸苯 基硫醚為佳。如前文中所提，聚合物基質實質上應與含矽 59243-930714.doc 1242029 氧烷添加劑不互容，但應不是完全與其不互容，因此不會 造成添加劑與聚合物基質完全分離。該聚合物基質必須熔 化使其與其中的添加劑混合，以及例如藉由模製將根據本 發明聚合物組合物製程所需物品的形狀。若添加劑在聚合 物基質的熔化溫度下是一種液體（即聚合物基質的熔化溫 度等於或高於添加劑的熔化溫度），則可幫助添加劑與聚合 物基質的混合。一個適合聚合物基質的實例是分子量從 150,000至1，000,000的聚伸苯基硫醚。 用於本發明之含矽氧烷添加劑具有羥基、烷氧基或環氧 基官能基和一個可與矽酮彈性體形成組合物之官能基鍵結 的官能基，其中矽酮彈性體形成組合物可藉氫矽烷基化反 應熟化。能與可藉氳矽烷基化反應熟化。能與可藉氫矽烷 基化反應熟化之矽酮彈性體形成組合物的官能基鍵結之官 能基實例包括烯基（如乙烯基、己烯-1-基）、炔基、烯丙基、 丙烯酸酯、曱基丙烯酸酯和與石夕鍵結的氫基。石夕氧烧最好 包含式RaXbSiO (4-a-b)/2 單元R代表烷基，最佳係曱基，X代表 氫、烯基（如乙烯基、5-己烯基）炔基、烯丙基、丙烯酸酯或 甲基丙烯酸酯基，a是1、2或3以及b是0、1或2，而且a+bS 3，其條件為矽氧烷分子包含至少一個X基。該矽氧烷可為 線性或環狀的。適合且具有這些官能基的添加劑實例是以 三甲基保護住末端的甲基氫矽氧烷和以三甲基保護住末端 的二甲基曱基（5-己烯基）矽氧烷。分子量較低的矽氧烷如這 些25°C時黏度為1000平方釐米/秒或更低，例如10至100平 方釐米/秒的矽氧烷在聚合物基質中比分子量較高的矽氧 59243-930714.doc 1242029 院更易具有較高的潛移性，此可能是一項決定石夕氧烧添加 劑的分子量並非決定性提供該添加劑可潛移至聚合物基質 表面以及實質上與其不互容，如上文中所討論般。矽氧烷 的分子量無下限如可使用二碎氧烧作為添加劑。 根據本發明聚合物組合物中所用的添加劑應作為塑膠物 品和矽酮彈性體間的連接物以提供其間的黏著力而且必須 不能與聚合物基質完全分離但與其必須維持某程度的鍵 結。此添加劑-聚合物基質鍵結必須是物理或化學鍵結，因 此除了具有與可藉氫矽烷基化反應熟化之矽酮彈性體形成 組合物鍵結的官能基之外，該添加劑包含一種具有經基、 烷氧基或環氧基官能基以與聚合物基質作化學性鍵結的矽 氧烷。本發明中用以與聚合物基質鍵結之較佳官能基為羥 基。所以用於本發明聚合物組合物中之較佳添加劑是末端 為羥基的曱基乙烯基矽氧烷，特別是25°C時黏度為20至40 平方釐米/秒之末端為羥基的曱基乙烯基矽氧烷。 利用一種石夕烧也可幫助含碎氧烧添加劑對聚合物基質的 鍵結，該矽烷具有適當的官能基可使其與添加劑和聚合物 基質兩者鍵結。如上文中所提及，與本發明中所用的聚合 物基質鍵結的官能基是羥基、烷氧基（如甲氧基、乙氧基） 和環氧基，較佳的石夕烧同時具有此種官能基和其他與添加 劑鍵結的官能基，即該^夕烧具有其他可與添加劑的官能基 鍵結的官能基，其中該添加劑的官能基可與藉氫矽烷基化 反應熟化之矽酮彈性體形成組合物鍵結。所以，當使用一 種含乙烯基-官能基的矽氧烷添加劑時，適合的矽烷為三甲 59243-930714.doc 1242029 氧基矽烷（（CH3〇）3SiH)，而當佶用人ς· u … “吏用的矽氧烷添加劑 呀，適合的矽烷為乙烯基二 / — T虱基矽焓 ((CH^LSiCH^CH?)。麥烧可右六★令， 】在添加劑加入聚合物基質之前 先與石夕氧烧添加劑預混合，或者可亩 ^ v 飞者了直接加入與矽氧烷添加 劑分開的聚合物基質中。 將從0.1至5.0重量％之聚合物基 Φ貝里之矽軋烷添加劑和 ，何附加的石夕烧一起加入聚合物基質中。低於〇ι%的添加 里無法提供足夠的添加劑以將矽酮彈性體黏至由本發明聚 合物組合物所形成的塑膠基質上，以及高於外的添加量: 導玫該塑膠基質因添加劑與聚合物基f之不相容性引起的 形態問題而造成破裂。精確的添加劑所需量將視特定添加 劑的特性和所用的聚合物基質而I但—般而t，添加劑 的量以從0.1至3重量％之聚合物美皙A ^ σ物暴貝為佳，最佳係從0.5至 2 · 0重量％之量。1242029 IX. Description of the invention: The present invention relates to a kind of XK compound composition comprising ^ '^ ^ ^ ^, which comprises a polymer matrix and an oxane-containing additive, and the composition can form a cured silicone elasticity. The body can be attached to a plastic object. From ^ σσ / 叩, especially a silicon cation elastomer cured by a hydrosilylation reaction, about a method for preparing a plastic article from the polymer composition, and about 3 Shixi oxidizing additives in the polymer combination The use of things. … Ideally, the syringone elastomer is coated on a plastic substrate. For example, in the field of sealing and gasketing, a loop made of a syringite can be formed on a plastic material. However, ‘Shi Xi_Elastomer ’s adhesion to plastic substrates is not good. For Shi Xi_Elastomer ’s adhesion to plastic substrates, it is often necessary to improve the phase elastomer and / or plastic substrate surface. Modification of the surface of lithophane elastomers and / or plastic substrates can usually be achieved by the use of adhesives, and the use of lithophyllum to achieve this goal. The improvement of the surface of the plastic substrate can be achieved, for example, by applying an adhesion promoter to the surface, or more generally by adding an adhesion promoter to the polymer matrix before it forms a plastic matrix. If the adhesion promoter is to be melted into the substrate ^, the adhesion promoter must be sneaked onto the surface of the polymer matrix if it is to promote its adhesion to the coated stone eve elastomer. We have found that when using a silane adhesion promoter, this creep does not always occur to a satisfactory degree, resulting in poor viscosity of the coated silicone elastomer. U.S. Patent Nos. 4,814,231 and 4,686,124 disclose thermoplastic resin-silicone composites wherein the resin contains an organohydrogenpolysiloxane such as a vinyl-terminated organohydrogenpolysiloxane to assist the resin in modifying the resin. Adhesion of cured silicone composition. 59243-930714.doc 1242029 In a first aspect, according to the present invention, there is provided a polymer composition comprising a polymer matrix and a silicone additive that is substantially incompatible with the polymer matrix, wherein the additive is a silicone It has a hydroxyl group, an alkoxy group or an epoxy group functional group and a functional group which can be bonded to a silicone elastomer forming composition, wherein the silicone elastomer forming composition can be cured by a hydrogen silylation reaction. Therefore, the present invention provides a polymer composition capable of forming a plastic article. The composition can be simply mixed with an additive and a polymer matrix melt, and then the polymer composition is formed to form a silicone elastomer which can be adhered thereto. Made of plastic matrix. The polymer composition according to the present invention additionally has the advantage that the plastic matrix made therefrom can be easily demolded compared to a plastic matrix made from a polymer melt containing no siloxane-containing additive used in the present invention. . The siloxane-containing additive used in the present invention is substantially incompatible with the polymer matrix. Here, `` substantially incompatible '' means that the additive will sneak to the surface of the polymer composition so that the additive combines with a silicone elastomer that can be cooked by hydrogen silylation reaction, but the additive and the polymer matrix Some compatibility is needed so that the additive does not completely separate from the polymer matrix. When the additive sneaks and then only bonds with the silicone elastomer and does not bond with the plastic matrix, it causes poor adhesion. Additives should act as a linker between the plastic matrix and the silicone elastomer molecule. Polymer matrices suitable for use in the polymer composition according to the invention are well known in the art and include polysulfone, polybenzene, polyetherketone, polyimine, polyester, polyethylene, polypropylene, and phenol Polyepoxy sulfide is preferred as the epoxy resin. As mentioned earlier, the polymer matrix should be substantially incompatible with the silicon-containing additive 59243-930714.doc 1242029, but it should not be completely incompatible with it, so that it does not cause the additive to completely separate from the polymer matrix. The polymer matrix must be melted to mix with the additives therein, as well as, for example, by molding the shape of the article required to process the polymer composition according to the invention. If the additive is a liquid at the melting temperature of the polymer matrix (that is, the melting temperature of the polymer matrix is equal to or higher than the melting temperature of the additive), it can help mixing the additive with the polymer matrix. An example of a suitable polymer matrix is polyphenylene sulfide having a molecular weight from 150,000 to 1,000,000. The silicone-containing additive used in the present invention has a hydroxyl group, an alkoxy group or an epoxy group functional group and a functional group capable of bonding with a functional group of a silicone elastomer forming composition, wherein the silicone elastomer forming composition Can be matured by hydrogen silylation. It can be matured by the reaction of thallium silylation. Examples of the functional group capable of bonding with the functional group of the silicone elastomer which can be cured by the hydrogen silylation reaction include alkenyl (such as vinyl, hexen-1-yl), alkynyl, allyl, Acrylates, fluorenyl acrylates, and hydrogen groups bonded to Shi Xi. The sintering of Shi Xi is best to include the formula RaXbSiO (4-ab) / 2. The unit R represents an alkyl group, and the most preferred fluorenyl group. X represents hydrogen, alkenyl (such as vinyl, 5-hexenyl), alkynyl, and allyl. Group, acrylate or methacrylate group, a is 1, 2 or 3 and b is 0, 1 or 2 and a + bS 3, provided that the siloxane molecule contains at least one X group. The siloxane may be linear or cyclic. Examples of suitable additives having these functional groups are methylhydrosilane with trimethyl protected terminals and dimethylfluorenyl (5-hexenyl) siloxane with trimethyl protected terminals. Lower molecular weight siloxanes such as these have a viscosity of 1000 square centimeters per second or lower at 25 ° C, for example, 10 to 100 square centimeters per second. 930714.doc 1242029 The hospital is more likely to have a higher potential for migration. This may be a factor that determines the molecular weight of the Shixi Oxygen Burning Additive. It is not critical to provide the additive with the ability to sneak to the surface of the polymer matrix and be substantially incompatible with it, as described above As discussed. There is no lower limit to the molecular weight of the siloxane. For example, dioxin can be used as an additive. The additives used in the polymer composition according to the present invention should act as a link between the plastic article and the silicone elastomer to provide adhesion therebetween and must not be completely separated from the polymer matrix but must maintain a certain degree of bonding with it. This additive-polymer matrix bond must be a physical or chemical bond, so in addition to having a functional group that forms a bond with a silicone elastomer that can be cured by a hydrogen silylation reaction, the additive contains a Siloxane with alkoxy or epoxy functional groups chemically bonded to the polymer matrix. The preferred functional group for bonding to the polymer matrix in the present invention is a hydroxy group. Therefore, the preferred additive for use in the polymer composition of the present invention is fluorenyl vinyl siloxane having a hydroxy end, especially fluorenyl ethylene having a hydroxy end at a viscosity of 20 to 40 cm2 / s at 25 ° C. Siloxane. The use of a stone fired sintering can also assist the bonding of the sintered oxygen-containing additive to the polymer matrix. The silane has suitable functional groups to allow it to bond to both the additive and the polymer matrix. As mentioned above, the functional groups bonded to the polymer matrix used in the present invention are hydroxy, alkoxy (such as methoxy, ethoxy), and epoxy groups, and the preferred Shi Xiyao has both Functional groups and other functional groups bonded to the additive, that is, the functional group which can be bonded to the functional group of the additive, wherein the functional group of the additive can be cured by the hydrosilylation reaction of the silicone The elastomer forms a composition bond. Therefore, when a vinyl-functional group-containing siloxane additive is used, the suitable silane is trimethyl 59243-930714.doc 1242029 oxysilane ((CH3〇) 3SiH), and when it is used by people… u The suitable silane additive is vinyl di-/-Tyl-based silicon enthalpy ((CH ^ LSiCH ^ CH?). Wheat can be burned to the right. ★ order,] before adding the additive to the polymer matrix The Shixi Oxygen Burning Additive is pre-mixed, or it can be added directly to the polymer matrix separate from the Siloxane Additive. It will be from 0.1 to 5.0% by weight of a polymer-based ΦBerry Silane Additive and The added Shi Xiyao is added to the polymer matrix together. The addition of less than 0% does not provide sufficient additives to adhere the silicone elastomer to the plastic matrix formed by the polymer composition of the present invention, and the high Addition amount outside: lead to the plastic matrix is broken due to morphological problems caused by the incompatibility between the additive and the polymer base f. The exact amount of the additive will depend on the characteristics of the specific additive and the polymer matrix used. IBut—general and t, The amount of the additive is preferably from 0.1 to 3% by weight of the polymer Mei Xi A ^ σ physalis, most preferably from 0.5 to 2.0% by weight.
在第二方面，根據本發明也提供—種製備塑膠物品的方 2 ’其中該塑膠物品有經氫钱基化反應熟化之㈣彈性 體黏於其上’此方法包括製備一種包含聚合物基質和實質 〃承σ物基貝不相容之含矽氧烷添加劑的聚合物組合 物，其中添加劑的石夕氧院具有經基、貌氧基或環氧基官能 基#個可與石夕綱彈性體形成組合物鍵結的官能基，其中 :酮彈性體形成組合物可藉氫矽烷基化反應熟化，將含矽 氧、元、加^和♦合物基質混合在一起，自該聚合物組合物 形成塑膠物品’將可經氫料基化反應熟化之㈣彈性體 〆成、且σ物塗復在塑膠物品上並且以氫矽烷基化反應熟化 59243-930714.doc -10- 1242029 矽_彈性體形成組合物。 可經氮碎燒基化反應熟化之矽酮彈性體形成組合物是已 的而且可商品取得，許多這類組合物也被描述於文獻 中適合的彈性體形成組合物包含至少一種具有脂族不飽 矛度之石夕氧烷聚合物和具有Si-H官能基之有機矽交聯劑。 亥石夕氧烧聚合物是具一般結構（H)之普通線性性質的聚有 機石夕氧烧 R， R， R, R，’In a second aspect, according to the present invention, there is also provided a method for preparing a plastic article 2 'wherein the plastic article has a rhenium elastomer cured by a hydrogenation reaction, and the method includes preparing a polymer matrix and Substantially incompatible polymer composition containing siloxane additives, in which the Shixi Oxygen Institute of additives has a functional group of a radical, an oxygen group, or an epoxy group, which has elasticity with Shixigang Functional groups bonded to the body-forming composition, wherein: the ketone elastomer-forming composition can be matured by hydrogen silylation reaction, and the silicon-containing oxygen, element, additive and compound compounds are mixed together, and the polymer is combined from the polymer. To form a plastic article 'is to form an elastomeric elastomer which can be cured by hydrogenation reaction, and the σ substance is coated on the plastic article and cured by the hydrogen silylation reaction. 59243-930714.doc -10- 1242029 silicon_elasticity Body forming composition. Silicone elastomer-forming compositions that can be cured by a nitrogen-based calcination reaction are available and commercially available. Many such compositions are also described in the literature. Suitable elastomer-forming compositions include at least one compound having an aliphatic compound. Saturated oxalate polymer and Si-H functional silicone cross-linking agent. Oxygen sintered polymer is a polyorganic stone sintered polymer with general linear structure (H). R, R, R, R, ’
I I I (Π) -Si-〇-[Si-〇]x.Si-RffI I I (Π) -Si-〇- [Si-〇] x.Si-Rff
I I I R， R， 其中R疋含南達18個碳原子的單價烴基，R”是含高達6個 厌原子的單彳貝煙基或氫原子，以及X是一個整數，例如從1 〇 至1500之值。以R,指含從個碳原子的烷基或芳基如甲 基、乙基、丙基、異丁基、己基、苯基或辛基為特佳。其 中較佳係所有R，基中至少5〇%是甲基，最佳係實質上所有 化是〒基。R”最好是選自一種脂族不飽和羥基或氫原子。 較佳係R”指含高達6個碳原子的烯基，最佳係適合氫矽烷基 化反應之乙稀基、炸丙基或己稀基。 有機矽交聯劑最好是選自矽烷類、低分子量有機矽樹脂 和紐鏈有機矽氧烷聚合物。該交聯劑化合物至少含有三個 與矽鍵結的取代基，該取代基可與描述於上之矽氧烷聚合 物之與矽鍵結的脂族不飽和烴基或氫原子R，，反應。在此聚 合物的R”基是一個烯基，交聯有機矽化合物上的反應性取 59243-930714.doc 1242029 代基最好是氫原子，使交聯有機石夕化合物和聚有機％b 間依照通用反應流程⑴進行氫㈣基化反應，其中r,，，是: 個二價烴基和y是〇或1。 myCH=CH2+H_Si^ ⑴ 適合的有機石夕交聯化合物包括主要由式Si〇i"_之四官处 基石夕氧烧單元和單官能基單元r,vR\Si()i/2所組成的有機= 樹月曰’其中R疋義如上’ R〇指一個與石夕鍵結的取代基，該 取代基可與描述於上之與石夕鍵結的脂族不飽和煙基或氣原 子R”反應，各具有一個從〇至3的值，v+w的和為3。適 T的短鏈有機嫩聚合物包括短鏈聚有機石夕氧院，其每 刀子：有至少3個與矽鍵結的氫原子’如含高達20個碳原子 之=二甲基石夕氧烧保護住末端的聚？基氫石夕氧烧以及四甲 基環四石夕氧烧。 除了矽氧烷聚合物和有機矽交聯化合物之外，彈性體形 :組合物最好也包含一種適合她基化加成反應的觸 _；最佳係、以族Vm金屬為基料的觸媒，如氯化始或者麵 或姥的化合物或錯合物。 其他可包含在適合的彈性體形成組合物中之附加成份包 、鏈延長劑、染料、助黏劑、著色劑、色素 '黏度 勺义劑、儲存壽命延長劑、抑制劑和撓曲劑。適合的填料 夕石 > 煙燻石夕石、煙霧狀石夕石、凝膠， 溶膠、二蓋 入/ ^ 、、磨碎的石英、磨碎經熟化的矽酮橡膠顆 碳酸舞和玻璃粉球。該填料最好如藉適合的石夕烧、短 錢脂肪酸或樹脂石夕剩物質等處理之使表面疏水。適 59243-930714.doc 12 1242029 合賦予填料表面疏水性的物質和程序已描述在文獻中而且 為熟諳此技著所熟知的。助黏劑包括環氧基、有機欽酸鹽 或月女基有機石夕化合物。在塑膠物品的成形和石夕綱彈性體黏 於其上之間也可使用底漆，適合的底漆包括含有機溶劑： 鈦酸鹽和石夕酸鹽及低石炭數石夕氧烧如八子基甲石夕氧垸。鏈延 長劑傾向為性質主要以線性為主而且在聚合物各端呈㈣IIIR, R, where R 疋 is a monovalent hydrocarbon group containing up to 18 carbon atoms, R ″ is a monopyridyl group or a hydrogen atom containing up to 6 anaerobic atoms, and X is an integer, such as from 10 to 1500 Value. R means alkyl or aryl group containing from one carbon atom, such as methyl, ethyl, propyl, isobutyl, hexyl, phenyl or octyl. Especially preferred is all R, groups At least 50% of them are methyl groups, and the best is substantially a methyl group. R "is preferably selected from an aliphatic unsaturated hydroxyl group or a hydrogen atom. "R" refers to an alkenyl group containing up to 6 carbon atoms. The most preferred is ethylene, propyl or hexyl suitable for hydrosilylation. The organosilicon crosslinker is preferably selected from silanes. , Low-molecular-weight organosilicon resins and new chain organosilicon polymers. The crosslinker compound contains at least three silicon-bonded substituents, which can be used in combination with the silicon described in the silicone polymer described above. The bonded aliphatic unsaturated hydrocarbon group or hydrogen atom R, reacts. The R "group of this polymer is an alkenyl group. The reactivity on the crosslinked organosilicon compound is preferably 59243-930714.doc 1242029. The hydrogen atom causes the hydrogenated reaction between the cross-linked organic stone compound and the polyorganic% b according to the general reaction scheme 其中, where r ,,, are: a divalent hydrocarbon group and y is 0 or 1. myCH = CH2 + H_Si ^ ⑴ Suitable organosilicone cross-linking compounds consist mainly of the oxygen-burning unit of the basic element of the formula Si〇i ”and the monofunctional radical unit r, vR \ Si () i / 2 Organic = Shuyue said 'where R 疋 is the same as above' R〇 refers to a substituent bonded to Shi Xi, which may be described with the aliphatic unsaturated nicotyl or gas atom bonded to Shi Xi R "reactions, each with a value from 0 to 3, and the sum of v + w is 3. The short-chain organic tender polymer suitable for T includes short-chain polyorganic stone oxygen institute, each knife: there are at least 3 and Silicon-bonded hydrogen atoms' such as those containing up to 20 carbon atoms = dimethylhydroxanthine to protect the terminal polyoxyhydroxanthine and tetramethylcyclotetraxanthine. In addition to siloxanes In addition to polymers and organosilicon cross-linking compounds, the shape of the elastomer: the composition preferably also contains a catalyst suitable for the basic addition reaction; the best catalyst, based on the group Vm metal, such as chlorination Compounds or complexes, starting or surface compounds, etc. Other additional ingredient packages, chain extenders, dyes that may be included in suitable elastomer-forming compositions Adhesion aids, colorants, pigments, viscosity extenders, shelf life extenders, inhibitors, and flexants. Suitable fillers > fuming stone, fuming stone, gel, sol, Two lids / ^, ground quartz, ground carbon dioxide and glass powder balls of cured silicone rubber. The filler is best to borrow suitable stone yaki, short-term fatty acids or resin stone residues, etc. Treated to make the surface hydrophobic. Suitable 59243-930714.doc 12 1242029 Substances and procedures that impart hydrophobicity to the filler surface have been described in the literature and are well known in the art. Adhesion promoters include epoxy groups, organic acetic acids Salts or moon-dried organic stone compounds. Primers can also be used between the molding of plastic articles and the adhesion of Shixun Elastomers. Suitable primers include organic solvents: titanates and oxalates And the low carbon number of stone oxidants such as octyl methyl oxalate oxonium. Chain extender tends to be mainly linear in nature and fluorene at each end of the polymer.
石夕鍵結之R。基的有機石夕氧烧物質，使其可與兩個氧烧聚I 物的R，’基反應，此僅延切氧烧聚合物的長度。 特佳的彈性體形成組合物包含一種每分子至少具有2個 ㈣鍵結的烯基’較佳係乙烯基之聚有機石夕氧貌、有機氫 交聯有機石夕組合物、以第vm族為基質的觸媒和填料。這 些成份在彈性體形成組合物中所佔的比例並無規定，雖然 烯基承有機石夕氧垸聚合物和含有與石夕鍵結之氫原子之有機 石夕父聯劑的存在量最好可確保每個烯基中至少包含—個與 石夕鍵結的氫原子，該比例較佳係從u/出/丨，最佳:、 至4/卜 一Shi Xi bond R. Based on the oxygen-burning material of the organolith, it can react with the R, 'groups of two oxygen-burning polymers, which only cuts the length of the oxygen-burning polymer. A particularly preferred elastomer-forming composition includes an alkenyl group of at least 2 fluorene bonds per molecule, preferably a vinyl polyorganic stone oxygen composition, an organic hydrogen cross-linked organic stone material composition, and a group vm. Catalysts and fillers for the matrix. The proportion of these components in the elastomer-forming composition is not specified, although the alkenyl-containing organosilicon polymer and the organospheric parent linker containing hydrogen atoms bonded to the silica are best present. It can be ensured that each alkenyl group contains at least one hydrogen atom bonded to Shi Xi. The ratio is preferably from u / out / 丨, and most preferably :, to 4 / bu.
I #措此合含石夕氧燒添加劑與聚合物基質物質可製備本發明 弟一方面之聚合物組合物。混合可藉任何此技藝中於此類 程序慣用的方式爽達占 、 ^ 武灭達成例如，一般可獲得丸狀的聚合物 基貝物^ 4丸狀物可被加人於加料漏斗中將其送入家 置〇戈t壓器中以加工這些丸狀物並形成塑膠物品 此種排列下，含石夕氧烧添加劑可被喷在加料漏斗中的丸狀 物 或者、、、二由一個進入口將其加入於該擠壓器中。該丸 狀物在擠壓器中炫化，其中含石夕氧烧添加劑與聚合物㈣ 59243-930714.doc -13- 1242029 熔化物混合形成根據本發明第一方面之聚合物組合物。在 文谷化過私和塑膠物品形成期間，含矽氧烷添加劑潛移至聚 合物組合物的表面。所以從聚合物組合物經擠壓可形成塑 膠物品。但是，當然其也可以其他此技藝中慣用的方式， 例如藉射出模製形成。當然，根據本發明第一方面之聚合 物組合物的丸狀物可以前文中所描述的方式預製備而成， 即可製備已包含含矽氧烷添加劑之聚合物基質物質的丸狀 物以供未來之使用。然後，此丸狀物可如此技藝中已知不 需要額外含石夕氧烧添加劑與其混合的步驟即可用於形成塑 膠物品。形成塑膠物品後，將可藉氫㈣基化反應熟化之 矽酮彈性體形成組合物塗覆在塑膠物品上並使矽酮彈性體 形成組合物熟化，以將該矽酮彈性體形成組合物塗覆在塑 膠物扣上，或者，例如藉共模製可同時形成矽酮彈性體和 塑膠物品。後者優於前者的優點是與兩個步驟方法相反之 -：步：的方法，雖然最適合使用的方法將視欲製物品的 性質而定。例最好在塑膠基f形成後，將碎氧烧彈性 體塾圈形成於其上。㈣彈性體也可經過後·熟化以進-步 改善其對塑膠物品的黏著力。 第-方面’本發明另外提供含石夕氧垸添加劑在具有經氮 矽烷基化反應熟化之矽酮彈性體黏於其上之塑膠物品梦備 二：其中切氧烧添加劑具有經基、烧氧基或環氧 土/月“和—個與可藉氫㈣基化反應熟化之石夕酮彈性體 形成組合物鍵結的官能基。 現在將以實例方式詳細描述本發明。 59243-930714.doc 1242029 實例 在第一個步驟中，聚合物組合物製備如下。 含矽氧烷添加劑A(定義如下）以表示於下面表丨之量和組 成與聚伸苯基硫醚（PPS)顆粒混合。第_種pps顆粒（τ_γ gsooppps]”）包含近2.0重量％之聚伸乙基壤脫模劑，而第 二種 PPS顆粒（Tedur· 92001 V2743-”PPS_2”）不包脫模劑。添 加劑A聚合物組合物可藉將添加劑噴在卩”-丨顆粒上而製 成。 然後將含PPS顆粒/矽氧烷之添加劑混合物送進一個射出 模製進料器中並加熱至顯示&下面们中t溫度以形成一 種聚合物熔化物。然後製備塑膠物品可藉將該聚合物熔化 物达入射出模製品形成—種自動引擎用的旋轉軸密封物而 製成。I # This combination of Shixi oxygen-containing additives and polymer matrix material can be used to prepare the polymer composition of the first aspect of the present invention. Mixing can be accomplished by any of the methods commonly used in this procedure in such arts, such as Shuangdazhan, Wuwu. For example, a pellet-like polymer-based shellfish can generally be obtained ^ 4 The pellets can be added to the addition funnel to mix them It is sent to a home press to process these pellets and form plastic objects. In this arrangement, the Shixian oxygen-burning additive can be sprayed on the pellets in the addition funnel or two, one, and two enter. Add it to the extruder. The pellets are glazed in an extruder, in which the sintered oxygen-containing additive and polymer ㈣ 59243-930714.doc -13-1242029 are melted to form a polymer composition according to the first aspect of the present invention. During the Wengu Chemical and plastic products formation, the siloxane-containing additive sneaks to the surface of the polymer composition. Therefore, plastic articles can be formed from the polymer composition by extrusion. However, of course, it can also be formed in other ways conventional in the art, such as by injection molding. Of course, the pellets of the polymer composition according to the first aspect of the present invention can be pre-prepared in the manner described above, that is, pellets containing a polymer matrix substance containing a siloxane-containing additive can be prepared for supply. Future use. This pellet can then be used to form a plastic article as known in the art without the need for an additional step of mixing it with a sintered oxygen-containing additive. After the plastic article is formed, a silicone elastomer-forming composition that can be cured by a hydrogenation reaction is coated on the plastic article and the silicone elastomer-forming composition is cured to coat the silicone elastomer-forming composition. Overlay on plastic buckles or, for example, co-mold to form a silicone elastomer and a plastic article simultaneously. The advantage of the latter over the former is that it is the opposite of the two-step method: the step: method, although the most suitable method will depend on the nature of the item to be made. For example, after the plastic base f is formed, a ring of crushed oxygen fired elastomer is formed thereon. ㈣Elastomers can also be post-cured to further improve their adhesion to plastic items. "-Aspect" The present invention also provides a plastic article containing a silicon oxide oxygen-containing additive adhered to a silicone elastomer which has been cured by a nitrogen silylation reaction. Dream preparation 2: wherein the oxygen-cutting additive has a thermal-based and oxygen-burning additive. Or epoxy clay / month "and a functional group bonded to the azulone elastomer that can be matured by a hydrofluorination reaction. The invention will now be described in detail by way of example. 59243-930714.doc 1242029 Example In the first step, a polymer composition was prepared as follows. Silane-containing additive A (defined below) was mixed with polyphenylene sulfide (PPS) particles in an amount and composition as shown in Table 丨 below. The _pps particles (τ_γ gsooppps] ") contain nearly 2.0% by weight of a polyethylenic soil release agent, while the second PPS particle (Tedur · 92001 V2743-" PPS_2 ") does not include a release agent. Additive A polymer composition can be made by spraying additives on the 卩 "-丨 particles. The additive mixture containing PPS particles / silicone is then fed into an injection molding feeder and heated to the display & The following t temperature is used to form a polymer melt. Then the plastic article can be prepared by forming the polymer melt into the molded product, a rotary shaft seal for automatic engines.
添加劑A=近30平方釐米/秒（在25 t:)末端為羥基的f基 細基碎氧烧。 ” Tedur”是Bayer A.G·的註冊商標。 在第二步驟中，為了形成矽酮彈性體以塗覆在先前所提 第個步驟中製成的旋轉軸密封物i，藉:¾合5 0份末端為 一甲基乙烯基二甲基矽氧烷（黏度近55,〇〇〇平方釐米/秒）、 25份二甲基乙烯基化和三甲基化矽石' 17份石英(以六甲基 59243-930714.doc 1242029 二矽氨烷和四甲基二乙烯基二矽氨烷處理過）、4份末端為 二甲基己烯基的二甲基甲基己烯基矽氧烷、2份含甲基 silsesqui〇xane之二甲基甲基氫石夕氧烧和含鉑觸媒以製備一 種可藉氫矽烷基化反應熟化的液體矽酮橡膠形成組合物。 如下面表2中所指示，在塗覆液體矽酮橡膠形成組合物之 ^ 將以八甲基四石夕氧烧為基料的底漆塗在部分塑谬物 品。在該組合物塗覆之前，先將啟動劑塗覆在液體矽酮橡 膠形成組合物欲塗覆其上之塑膠物品部分上。然後將橡膠 形成組合物射出模製成塗覆底漆的或未塗覆底漆的塑膠物 品，並在下面表2中所指示之溫度和熟化時間中熟化。然後 如表2指示般，部分液體矽酮橡膠密封物在16〇。(：下後-熟化 1小時。Additive A = f-based fine-based crushed-oxygen burning with a hydroxyl group at the end of nearly 30 cm2 / s (at 25 t :). "Tedur" is a registered trademark of Bayer A.G. In the second step, in order to form a silicone elastomer to coat the rotary shaft seal i made in the first step mentioned above, 50 parts of the end is monomethyl vinyl dimethyl silicon Oxane (viscosity close to 55,000 cm2 / s), 25 parts dimethyl vinylated and trimethylated silica '17 parts quartz (as hexamethyl 59243-930714.doc 1242029 disilazane And tetramethyldivinyldisilazane), 4 parts of dimethylmethylhexenylsiloxane terminated with dimethylhexenyl, 2 parts of dimethyl containing methyl silsesquioxane Oxygen firing of methylhydroxan and platinum-containing catalysts are used to prepare a liquid silicone rubber forming composition which can be cured by a hydrogen silylation reaction. As indicated in Table 2 below, when a liquid silicone rubber-forming composition is applied, a primer based on octamethyltetraxane is applied to a portion of the plastic article. Before the composition is applied, the initiator is applied to the portion of the plastic article to which the liquid silicone rubber-forming composition is to be applied. The rubber-forming composition is then injection molded into a primed or unprimed plastic article and cured at the temperatures and curing times indicated in Table 2 below. Then, as indicated in Table 2, a portion of the liquid silicone rubber seal was at 160. (: After the next-ripening for 1 hour.
泛些根據本發明之聚合物組合物實例和方法顯示液體矽 鋼橡膠如何黏在由該聚合物組合物所製成的塑膠物品上， 若〃對由不3 έ矽氧燒添加劑之該聚合物組合物所製成的 塑膠物品缺乏黏性之液體矽酮橡膠相比。這些實例也說明 本發明的其他優點’其中可省略底漆的使用而液體石夕嗣橡 膠可對塑膠物品保持良好的黏著力。 59243-930714.doc -16-Some examples and methods of the polymer composition according to the present invention show how liquid silicon steel rubber adheres to plastic articles made from the polymer composition. Compared with liquid silicone rubber, plastic articles made of plastics lack viscosity. These examples also illustrate other advantages of the present invention ', in which the use of a primer can be omitted and the liquid stone rubber can maintain good adhesion to plastic articles. 59243-930714.doc -16-